Making gasolene substitute



C. ELLIS.

IVIAKING GASOLENE SUBSTITUTE.

APPLICATION FILED OCT. 4I 1913.

C. ELLIS.

MAKING GASOLENE SUBSTITUTE.

APPLICATION FILED OCT. 4. I9I3.

I,39@999 IamIeI Nov. I5, IIIZII.

3 SHEETS-SHEET 2.

C. ELLIS.

MAKING GASOLENE SUBSTITUTE.

APPLlcATIoN FILED ocTz 4Y 1913.

LSQQQQ, Patented Nov. 15, 1921.,

neaaaee.

To all whom it may concern:

lBe it known that I, CArLn'roN ELLIS, a citizen of the United States, and a resident of Montclair, in the county of Essex an'd State of New Jersey, have invented certain new and useful llmprovernents in Making Gasolene Substitutes, of which the following is a specihication.l

This invention relates to a process of making gasolene from heavier oils such as kerosene and the like and is related in particular to a system or organization of correlated elements; the whole forming an integral process or organization whereby rom heavier oils there may be obtained lighter fractions akin to or suitable for use in place of ordinary gasolene.

ln -order to render the nature of the organization clear, lf have appended two plans Y showing the path of material undergoing treatment, this being indicated by Figures 1 sind 2; while Fig. 3 shows a structure suitable for carrying out the procedure indicated by Fig. 1 and Fig. 4 apparatus for carrying out the procedure'indicated by Fig. 2.` Fig. 3 is shown mainly in sectional elevation, and, in a diagrammatic mannen' shows the heating and condensing system and stabilizing means adapted for carrying out the present system. Fig. 4 shows in a diagrammatic manner a modified form of the apparatus illustrated in Fig. 3 including' also additional apparatus hereinafter referred to in the description .of the process indicated by Fig. 2. F ig.v 5 is a detail sectional View of one of the decomposing tubes showing the manner in which the material is placed therein.

By referring to Fig. 1 it will be noted that the first member is a decomposer or decomposing tubes. This element may'consist of a series of tubes placed in a'furnace and adapted to be heated to a temperature of L1GO-600" C. or so, while the heavier oil passes through in the form of a vapor and is subjected to thermal decomposition during such travel. Uf course, be long or short according of travel of the oil vapors with respect to the temperature of the surrounding gases applied for heating such tubes. linto the decomposer may be admitted along with the oil oroilvapors a quantity of steam so as Specicatlon of Letters Patent.

- preferably is employed catalytic G GASOLENE SUBSTITE.

to provide .20-50% of water more or less, based on the nature of the oil employed. lin place of a tubular structure a retort or still may be employed. lin the decomposing tubes l preferably place catalytic'material, preferably metal. bodies of a shape adapted to formbafHing surfaces while permitting a ready How of the vapor.

Metal which is a good conductor of heat conduction to prevent a coldcore of gases along the m1ddle of the tube rendering that art of the 4tube without eective action.

.url'ng the first part of the travel of the o1l vapors for, e'ective action ll preferably bring them into contact with surfaces of copper andin the latter part of the travel with surfaces of nickel. This may be accomplished by' plating jackston'es and the like withcopper or' respectively with nickel and packmg the tubes with the jack stones whlch pack in such a way that the greatest battling eHect is secured at the center and most rapid travel at the 'circumference of the tube which, of course, is hottest and selves and more or less stabilization with establishment of certain conditions of equilibrium which could not be secured satisfactorilv in the decomposing tubes where strong heat is being applied externally.

The decomposition products contain unstable constituents which, in the digester, react with the gases present and particuthetubes maytlarly hydrogen, or with each other or by to the velocity.

polymerization, to produce more stable Patented Nov.. l5, temi. application llled october il, 211913. erlal tto. 793,377.

in order by rapid compounds in substantial 'molecular equilibrium.4 From the digester the vapors may go to a dephlegmator or fractioning column which preferably 1s of a type used in the rectification of alcohol and the like in place of the ordinary coarse dephlegmator used in the present day rectification of oil. In the deplilegmator or fractioning column the heavy oil is condensed and if desired a dephegmator may be arranged to yield as fractions a gas oil and unconverted kerosene especially if the latter is employed as the raw material. Preferably, however, the kerosene is separated from the heavier oils and the former returned to the decomposing tubes While the latter which is preferably separated as a fraction similar to gas oil, is collected `and suitable disposition made thereof.

The lighter oils or-volatile spirits are not condensed in the dephlegmator and preferably passed into a desulfurator which may be a tube containing copper filings or copper oXid or other metallic or non-metallic desulfuring agent maintained at a temperature suitable for satisfactory desulfurization. Preferably, however, a desulfuring agent similar to that employed in the subsequent process of hydrogenation is made use of.

Oils which have been purified for the market such as; for example, ordinary lamp oil or kerosene contain very little sulfur as a rule, but enough is usually present to affect the catalyzer employed in the hydrogenation step which is subsequently to be described, and in that case the sulfur has to be removed in order to secure a catalyzer of sufficient endurance. When using a catalyzer such as nickel or cobalt, traces of sulfur or chlorin act in a poisonous manner rendering the c atalyzcr in a short time wholly inert. Oils which have been sufficiently desulfurized for commercial purposes often have enough sulfur or other toxic agents to decrease the catalytic activity, because of the great sensitiveness of these catalytic bodies to catalyzer poisons. Hence if .nickel is employed as a catalyzer, preferably"v the spent nickel catalyzer, that 1s to say the catalyzer which has lost its catalytic activity, may be employed for removing those traces of divers bodies which act poisonously. While copper oxid and the like lwill remove sulfur in a commercially satisfactory Way, it is better, as stated, when removing sulfur. to fitv an oil for catalytic hydrogenation to use as a desulfurizing agent the catalyzer itself or spent masses of the same, as thereby the specific selective action of the metal and removal of the particular traces of sulfur or other toxic agents acting on the catalyzer is satisfactorily effected, which oftentimes may not be the case when using metals or compounds of dissimilar affinities for the sulfur and other toxic agents.

The" product having been suitably prepared "in this or other manner for ydrogenation, it is now preferably passed through a hydrogenating 4apparatus in which it contacts with nickel or other catalyzer in the presence of hydrogen. The nickel is preferably carried on a support of the nature of crushed glass or other dense impermeable material. The glass is preferably fairly uniformly plated with a very thin layer of nickel material. A temperature between 20G-300o C. preferably is maintained in the hydrogenator during the operation. The product then passes to a condenser where itmay be obtained in a suitable form for the market or, if desired, may be re-distilled or treated with sulfuric acid and alkali or subjected to any other method of treatment, although in general it is sufficient to simply pass the product through the hydrogenator in order to add hydrogen and thereby satisfy the unstable bodies present, as this usually affords a product of good color, odor and stability.

In Fig. 2 the light fraction passes from the dephlegmator uncondensed, the lighter oils and gases being mingled; while according to the plan of Fig. 1, the gas may be removed from the condensed light oils at the dephlegmator. The uncondensed vapors may then pass to a desulfurator and through a temperature regulator where the temperature of the vapors may be adjusted to about 240 C. whereupon they ma'y be introduced into the hydrogenator wherein the free hydrogen contained in the gases of decomposition from the decomposing tubes may be caused to unite with the oil vapors. Hydrogen, of course, may be supplied from an external source in the amount required. The product passes into a condenser and the light oils are thus obtained in a liquid form, whilev any excess of hydrogen and the other gases which are resent containing entrained vapors may be passed to a cornpressor or scrubber or washer or refrigerator Where any useful light oils may be recovered.

A similar operation may be employed in the case of the gas derived acording to the system indicated in Fig. 1. These gases may then be passed through a gas decomposer where they are subjected to a Very high temperature in order to break down the hydrocarbons into the carbon and hydrogen and after suitable washing or other purication the hydrogen may be returned to the hydrogenator, as described in connection with Fig. 2.

In Fig. 3, 1 is a furnace structure containing a. battery of heating tubes as shown at 4, 4", 4b, and 4. These consist of pipes set horizontally or practically so, connected end to end in such a manner as to form a continuous passage from the up erhorizontal tubes to the lower ones. lIhey are heated by fuel gas supplied through the pipes 2. 3 is a chimney for the spent gases or products of' combustion. The tubes 4, 4, 4b, 4c, may be filled with catalytic and heat-conducting material as shown at 3 (Fig. 5), the uppermost pipes preferably containing copper fragments and the lowermost preferably carrying nickel bodies. A feed-pipe 5 serves for the introduction of oil, oil vapor, oil and water, steam and oil, or the vapors of steam and oil. As shown, a branch pipe 5 may be provided for the introduction of steam or water, the pipe being provided with a suitable valve to permit regulation of the proportions of oil or oil vapor and water or steam. These pass down- Wardly through the several series of heating pipes and then by risers 6, 6"', 6b, and 6c, are taken to the manifold 7 which communicates with the digester drum 8. This drum is preferably of considerable length in reference to the diameter and has an inlet for the oil vapors at one end, while the outlet represented in the drawing by 9 preferably is at the other end. The products of combustion from the heaters below the decomposing tubes pass up and around the' drum and in some cases may add heat to it and in other cases may serve more as an insulating blanket of heated air to prevent any substantial drop of temperature in the digester 8.

The slow travel of the vapors through the drum enables molecular equilibrium to be established to a considerable degree. The pipe 9 leads to a dephlegmator 10 which may be a column apparatus of a type adapted to make fairly sharp separation of close boiling fractions. These may be withdrawn at 11, 11a and 11b. A pipe 12 carries the light distillate to a desulfurizer 13 which preferably is filled with spent nickel catalyzer. Gases are withdrawn by the pipe 15 which carries the valve 16. 14 is a trap which enables the gases to be collected at that point. 17 is a pipe leading to the hydrogenator 21. The pipe 17 carries the valve 18. 19 is a pipe serving to introduce hydrogen or other suitable reducing gas, the flow of which therethrough being regulated by the valve 20. A flue 22 conducts gases from the-stack 3 to the hydrogenator 21 in order to furnish heat for the latter, air being admitted to the hydrogenator by openings, whereby suitable control of temperature is secured which preferably shouldy be between 240-250O C. The hydrogenator as shown consists of a series of tubes 24 connected to form a continuous passage, in the tubes being placed nickel or other catalyzer, but preferably nickel plated or coated on dense impermeable fragments or granules of such a character as to prevent the vapors from permeating the support. The temperature of the hydrogenator may be re ulated by admitting any desired quantity o air in addition to the products of combustion from the pipe 22. As shown, the casing 21 is provided with openings 21 and shutters or valves 22 are arranged over these openings to permit regulation of the air feed. Thus recovery of the catalyzer when as such it can no longer be used, is made possible, which is difficult when the metal is lodged inside a porous carrier as would be the case with a porous support, causing trouble in regeneration. From the tubes 24, the light oil products are conveyed to a condenser 25 where any remaining condensable fractions are liquefied. The finished product is removed from the condenser by outlet 26, and may be delivered to a separator 26 for the purpose of removing any excess water. The material obtained from the outlet 26 or the separator 26 is composed of low boiling saturated hydrocarbons of the nature of gasolene. From the tubes 24 of the hydrogenator 21 the product passes through the condenser 25- provided with the valved out-v let 26.

Porous bodies sometimes show a tendency to selectively absorb some portion of the oil, thus tending to clog the catalyzer. Also in the preparation of the catalyzer with a porous support, it is difficult owing to an occclusive force to free suchv catalyzer from objectionable impurities by washing. Again there is the difficulty of securing a satisfactory coating of materials; so for these and for other reasons a carrier of the nature of glass or metal preferably is employed as a support. Thus iron, copper and aluminum and the like may be employed.

Tn the somewhat modified form of apparatus shown in Fig. 4, employed in carrying out the procedure indicated by Fig. 2, a temperature regulator 17a having an inlet 17b and an outlet 17 c for a suitable temperature regulating fluid is preferably connected in pipe 17 between the desulfurlzer 13 and the hydrogenator 21. The temperature of the 110 .vapors is preferably adjusted in the temperature regulator 17a to about 2400 C. In this form of apparatus the valved outlet 26 from the condenser 25 is connected with a trap 27 where the light oils may be obtained 115 in liquid form and drawn off through the valved outlet 28. The uncondensed gases may advantageously pass through pipe 29 to a scrubber or washer 30 then through the valved connecting pipe 31 to a refrigerator 120 32 then through pipe 33 to a compressor 34 from which the uncondensed portion of the product is returned through valve pipes 35 and 19 to the hydrogenator 21 as hereinabove described in connection with Fig. 2,

` one of several locations and may be omitted when the oil is sufficie'f' free from toxic bodies to have no substantial or objectionable effect on the catalyzer. When water is used in the decomposing tube and an excess is employed this will appear later, on condensation and suitable means should be provided for its removal. The apparatus is preferably run at a slight pressure although a considerable pressure, as several atmospheres may be employed if desired.

The foregoing description of the present system of treatment is not to be construed as a limitation by virtue of any detail herein specified as various deviations therefrom will now be evident to those skilled in this art. For example, various elements may be eliminated under due circumstances, such as the desulfurizer when the-oil is at the start sufficiently free from sulfur poisons. Or various elements may be added to the present system,` or hydrogenation of the unsaturated components may take place in the liquid state, instead of in the vapor state as specified; the-oil ythen for example being contacted under pressure with finely-divided catalyzer as hydrogen is caused to pass through or Contact with the oil while the catalyzer is maintained well intermingled with the oil by any suitable means.

What I claim is:

l. The system of making a gasolene substitute which comprises passing a kerosene or heavier oil through a heated zone wherein decomposition of the oil takes place, in passing the products of decomposition into a digestion chamber and exposing said vapors to digesting conditions, fractionating to remove the heavy fractions, desulfuring the light fractions and hydrogenating same.

2. The system o-f making gasolene substitute which comprises passing kerosene material through a heated zone in the presence of heat-conducting and catalytic material, in allowing the decomposed material to inter-react to establish equilibrium by digestion, in fractionating same, in collecting the light oil, removing any toxic traces of sulfur present and in hydrogenating the product. f

3. The system of making a gasolene sub-b stitute which comprises passing kerosene vapors and the like admixed with the vapors of steam through a long passage way heated to a temperature between 40G-600 C. and containing first a quantity of metal material comprising copper and second in series a quantity of metal material comprisingl nickel, in withdrawing the products of de composition, passing same into and through a digester of great length in order to establish equilibrium in part, in fractionating, in collecting the heavy oil as gas oil and kerosene onthe one hand and light volatile oil on the other hand7 in removing any toxic traces of sulfur from the light volatile oil, and in combining hydrogen with said light volatile oil.

4. The system of making a gasolene sub stitute which comprises passing kerosene vapors and the like admixed with the vapors of steam through a long passage way heated to a temperature between 40045000 C. and containing first a quantity of metal material comprising copper and second a quantity of metal material comprising nickel, in Withdrawing the products of decomposition and passing these through a digestion conduit of great length, inv fractionating, in collectn ing the heavy oil as gas oil and kerosene on the one hand and light volatile oil on the other hand, in removing any toxic traces of sulfur from the light volatile oil, and in combining hydrogen with said light volatile oil.4

5. The system of making av gasolene sub` stitute which comprises passing oils heavier than gasolene through a heat decomposing zone, in digesting the products of decom position for a protracted period whereby stable saturated bodies are formed, in fractionating to remove the heavier oils, in colF lecting the uncondensed vapors of light oils and accompanying gases, in passing same through a desulfurizer to remove traces of toxic bodies, in adjusting the temperature to approximately 24m-2500 C., in passing the vapors and gases through a mass of nickel material in the presence of hydrogen, in condensing the light volatile oil stabilized by hydrogenation, in collecting the gases and removing therefrom the entrained vapors, in combining the very light oils thus secured or any suitable portion thereof with the aforesaid light oils coming from the condensing apparatus, in submitting some portion at least of said gases to a high temperature, whereby decomposition of hydrocarbons takes place, in freeing the hydrogen thereby secured from objectionable impurities and returning same to the zone of hydrogenation.

6. The system of making a gasolene sub-v stitute which comprises passing oilsheaviei than gasolene through a heat decomposing zone, in stabilizing by digesting the products of decomposition, in fractionating to remove the heavier oils, in collecting the uncondensed vapors of light oils and accompanying gases, in passing same through a desulfurizer to remove traces of toxic bodies, in adjustingV the temperature to approximately 24U-2509 C., in passing the vapors and gases through a mass of nickel material in the presence of hydrogen, in condensing the light volatile oil stabilized by hydrogenation, in collecting the gases and removing therefrom the entrained vapors, in

combining the' very light oils thus secured light oils coming from the condensing apparatus, in submitting some portion at least of said gases to a high temperature, whereby decomposition of hydrocarbons takes place, in freeing the hydrogen thereby secured from objectionable impurities and returning same to the zone of hydrogenation.

7. The system of making a gasolene substitute which comprises passing oils heavier than gasolene through a heat decomposing zone, 1n fractionating to remove the heavier oils, in collecting the uncondensed vapors of l light oils and accompanying gases, 1n saturating these in part by digesting causing interaction and formation of more stable products, in passing the vapors and gases through a mass of nickel material in the presence of hydrogen, in condensing the light volatile oil stabilized by hydrogenation, in collecting the gases and removing therefrom the entralned vapors, in combining the very light oils thus secured or any suitable portion thereof with the aforesaid light oils coming from the condensing apparatus, in submitting some portion at least of said gases to a higher temperature, whereby decomposition of hydrocarbons takes place, in freeing the hydrogen thereby secured from objectionable impurities and returning same to the zone of hydrogenation.

8. The process of producing gasolene-like material from heavier oil which consists in heating it to the decomposition temperature of the principal constituents thereof, dlgesting the resulting decomposition products f by holding such products Without the substantial loss of heat so that they react upon themselves, and hydrogenating the gasolenelike material produced.

9. The process of producing gasolene-like material from heavier oil which consists in heating it to the decomposition temperature of the principal constituents thereof, digesting the resulting decomposition products by holding such products Without the substantial loss of heat so that they react upon themselves, and hydrogenating the gasolene-like material produced by subjecting it to the action of hydrogen in the presence of a catalyzer carried by non-porous material, at an elevated temperature.

10. The process of producing gasolene-like material from heavier oil which consists in heating it to the decomposition temperature of the principal constituents thereof, digesting the resulting decomposition products by holding such products without the substantial loss of heat so that they react upon themselves, and hydrogenating the gasolenclike material produced by subjecting it to the action of hydrogen in the presence of nickel plated upon a vitreous support, at an elevated temperature.

11. The process of producing gasolene-like material from heavier oil which consists in heating it to the decomposition temperature of the principal constituents thereof, digesting the resulting decomposition products, by holding such products Without the substantial loss of heat so that they react upon themselves, removing catalyzer poisons from the gasolene-like material produced and hydrogenating such gasolene-like material.

12. The process of producing gasolene-like material from heavier oil which consists in heating it to the decomposition temperature of the principal constitutents thereof, digesting the resulting decomposition products, removing catalyzer poisons from the gasolenelike material produced, by the action of spent catalyzer and hydrogenating the thus purified product.

13. A stabilized gasolene-like product comprising digested and hydrogenated volatile petroleum material.

14. A gasolene-like product comprising digested and hydrogenated decomposition products of petroleum oil.

Signed at Montclair in the county of Essex and State of New Jersey this 2nd day of October, A. D. 1913.

ACARLEIFON ELLIS. 

